Solar Energy 215 (2021) 346–355

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Environmental performance of dye-sensitized solar cells based on

natural dyes
Alfred Błaszczyk a, *, Katarzyna Joachimiak-Lechman b, Sylwia Sady a, Tomasz Tański c,
Marek Szindler c, Aleksandra Drygała c
a
Department of Natural Science and Quality Assurance, Poznań University of Economics and Business, al. Niepodległości 10, 61-875 Poznań, Poland
b
Department of Quality Management, Poznań University of Economics & Business, al. Niepodległości 10, 61-875 Poznań, Poland
c
Department of Engineering Materials and Biomaterials, Silesian University of Technology, Konarskiego 18A, 44-100 Gliwice, Poland

A R T I C L E I N F O A B S T R A C T

Keywords: Dye-sensitized solar cells (DSSCs) are promising alternatives to silicon-based solar cells due to their compatibility
Life cycle assessment (LCA) with flexible substrates and their ability to work under low-light conditions. The performance of these solar cells
dye-sensitized solar cells (DSSCs) mainly depends on the sensitizer structure. Sensitizers based on synthetic dyes typically exhibit the best con­
Natural dyes
version efficiency; however, they have many problems such as scarcity of metals, lengthy purification steps, high
Chokeberry
synthesis costs, and high environmental impact. Natural dyes extracted from plants have been proposed as al­
ternatives due to their nontoxicity, facile preparation, and low production cost, although they have lower effi­
ciencies. This study used a life cycle assessment (LCA) metohodology to investigate the environmental
performances of DSSCs based on natural sensitizers. We fabricated three DSSCs based on natural dyes, obtained
from the juice, pomace, and leaves of black chokeberries, and another with synthetic N719 sensitizer. The results
showed that the photovoltaic module containing synthetic N719 dye had the lowest environmental impact
among all analyzed impact categories. Among the modules containing natural dyes, cells with chokeberry juice
dyes had the highest environmental performance.

1. Introduction scarcity of metals, lengthy purification steps, and high environmental

Dye-sensitized solar cells (DSSCs) are promising alternatives to
silicon-based solar cells and have been extensively studied in recent
years due to their expected cost-effectiveness, tunable transparency,
compatibility with flexible substrates, and ability to work under low-
light conditions (Fakharuddin et al., 2014). The performance of DSSCs
mainly depends on the molecular structure of the dyes used as sensi­
tizers, which separate electrons and holes upon excitation by light.
Since the work of O’Regan and Grätzel (1991), many transition metal
complexes (Bignozzi et al., 2013; Polo et al., 2004) and metal-free
organic dyes (Błaszczyk, 2018; Chaurasia and Lin, 2016; Zhang and
Cole, 2015) have been used as sensitizers. By utilizing metal-complex
sensitizers, the power conversion efficiencies of DSSCs have reached
14% (Kakiage et al., 2015; Yella et al., 2014). Different types of synthetic
dyes, such as metallic complexes, porphyrins, and organic molecules,
have shown the best conversion efficiencies (Shalini et al., 2016; Sharma
et al., 2018), but they have many problems, such as a high synthesis cost,
impact (Misra et al., 2009). On the other hand, sensitizers based on dyes
extracted from plants and bacteria are non-toxic, can be easily extracted,
and easily prepared, with even lower production costs despite their
lower efficiencies (Ashok et al., 2018; Iqbal et al., 2019; Ludin et al.,
2014; Silva et al., 2019). The most common natural photosensitizers
extracted from plants belong to carotenoids, anthocyanins, betalains and
chlorophylls have been recently investigated (Obi et al., 2020; Calogero
et al., 2018; Iqbal et al., 2019; Erande et al., 2020). However, until now
DSSCs based on natural sensitizers had solar to electric conversion ef­
ficiencies less than 3% (Omar et al., 2020; Iqbal et al., 2019). Hitherto
different strategies to improve the efficiency and stability of DSSCs with
natural sensitizers have been explored such as: selective purification by
column chromatography (Wang et al., 2007a, 2007b), selective extrac­
tion (Calogero et al., 2018), the mixing with other natural dyes (Obi
et al., 2020; Wang et al., 2007a) and different types of electrolyte ad­
ditives to suppress the dark current (Calogero et al., 2015). For example,
the performance of anthocyanin-DSSCs were improved after removal of

* Corresponding author.
E-mail address: alfred.blaszczyk@ue.poznan.pl (A. Błaszczyk).

https://doi.org/10.1016/j.solener.2020.12.040
Received 29 September 2020; Received in revised form 13 December 2020; Accepted 15 December 2020
Available online 18 January 2021
0038-092X/© 2021 International Solar Energy Society. Published by Elsevier Ltd. All rights reserved.
A. Błaszczyk et al.
organic compounds (non-pigments). Moreover, solar cells sensitized
with the anthocyanin and betalain blend showed the higher efficiency
and improved photostability over those sensitized with separated dyes
(Calogero et al., 2012; Prabavathy et al., 2017; Ramamoorthy et al.,
2016). The choice of a suitable solvent for extraction of natural pigments
have influence on stability of DSSCs sensitized with annatto carotenoid
and improved energy efficiency up to 1.6% (Calogero et al., 2018).
There are several possible chemical functional groups that are able to
bind the natural sensitizer to the semiconductor. Natural dyes equipped
with carboxylic groups provide a stronger electronic coupling to semi­
conductor and better interaction with redox couple (Calogero et al.,
2012). It has been proved that the interaction between semiconductor
film and carboxylic groups leads to an advantageous anchoring of the
dye to the TiO2 semiconductor due to the formation of a quasi-covalent
linkage of the carbonyl group of the dye with the TiO2 surface, mediated
by a shared proton (Tabacchi et al., 2019).
Among edible fruits, black, blue, and purple berries and their leaves
are one of the most important sources of polyphenols, such as phenolic
acids, anthocyanins, flavonols, and proanthocyanidins (Fig. 1) (Wu
et al., 2004). All of these molecules absorb visible light and have o-
hydroxychinon moiety necessary to bind to the semiconductor nano­
structure to transfer electrons from molecules to the conduction band of
porous semiconductor films after absorbing light.
Interestingly, black chokeberry (Aronia melanocarpa) has the highest
production of any edible berry in Poland and contains high amounts of
phenolic acids, anthocyanins, flavonols, and proanthocyanidins, espe­
cially in its skin (Oszmiański and Wojdyło, 2005; Wathon et al., 2019)
(Fig. 1). Fruit pomace is a by-product of wine/juice production, and
some studies have shown that chokeberry leaves are also a great source
of chlorophylls and phenolic compounds (Tian et al., 2017). However,
no study has investigated the influence of chokeberry juice, pomace, and
leaf extracts on the photovoltaic parameters of DSSCs.
Although DSSCs are considered a renewable energy source, they still
have an environmental impact. To completely assess the net environ­
mental benefits of DSSCs, it is necessary to conduct an environmental
life cycle assessment (LCA). Based on the definioton, LCA involves
compilation and evaluation of the inputs, outputs and the potential
environmental impacts of a product system throughout its life cycle (ISO
14040:2009). As mentioned, it considers inputs and outputs such as
energy, materials, waste, and emissions (Fthenakis and Kim, 2011).
There have been only a few LCA studies on DSSCs (Greijer et al., 2001;
Parisi et al., 2011, 2014), but no LCA has been performed on DSSCs
based on natural dyes.
Therefore, the goal of this paper is to assess the environmental per­
formance of DSSCs based on natural sensitizers and to compare the
environmental performance of DSSCs containing natural dyes and
a) b)
TiO2
O O
ROOC O O
TiO2
HO O HO
O OR
OR
OH
R: sugar moieties
Fig. 1. Chemical structures connected to the TiO2 semiconductor of commonly occurring: (a) phenolic acids, (b) anthocyanins, (c) flavonols, (d) proanthocyanidins
in the black chokeberry.
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Solar Energy 215 (2021) 346–355
synthetic N719 dye using the LCA methodology. To accomplish this, we
fabricated three DSSCs based on natural dyes obtained from the juice,
pomace, and leaves of black chokeberry, and another with synthetic
N719 sensitizer.
2. Materials and methods
2.1. Goal and scope definition
The aim of this study was to assess and to compare the environmental
performance of DSSCs containing natural dyes and synthetic N719 dye
in order to determine whether replacing the synthetic N719 dye with
natural dyes is environmentally sound. We also sought to identify the
hot spots of the analyzed DSSCs. Four different laboratory-produced
dye-sensitized solar devices were considered (Fig. 2).
The defined functional unit is to supply 1 kWh of electricity with
standard parameters with a lifetime of 1 year. To calculate amount of
electrical energy (E) produced by DSSCs the following equation was
applied:
η∙I∙AA∙PR
E=
ε
where: η is energy efficiency of solar cell [%]; I is the average yearly
irradiation [kWh⋅m− 2⋅year− 1]; AA is active area [m2]; PR is the per­
formance ratio; ε is the electrical conversion factor [%].
Taking into account the efficiency of the fabricated devices and the
climate specificity in Poland (I = 1000 kWh/m2 per year), the following
reference flows were determined:
▪ 0.13 m2 module containing cells with N719 dye,
▪ 4.62 m2 module containing cells with dyes from chokeberry
juice,
▪ 6.38 m2 module containing cells with dyes from chokeberry
pomace extract,
▪ 5.36 m2 module containing cells with dyes from chokeberry
leaf extract.
The system boundaries that were analyzed in the LCA study included
phases from raw material extraction to the factory gate (Fig. 3).
As part of the study, the production processes of the main photo­
voltaic cells components dye, TiO2 paste, platinum paste, electrolyte,
and FTO TEC7 glass were taken into account, as was the manufacturing
process of the module containing 10 cells with a total area of 0.00625 m2
(Table 1). The manufacturing process omitted the encapsulation stage,
and the details are described in Section 2.3.1.
c) d)
TiO2
TiO2 O
O
O HO O
O OH
OH
OH
OR HO O
OH O
OR
OH
A. Błaszczyk et al. Solar Energy 215 (2021) 346–355

Fig. 2. Schematic diagram of the DSSC assembly and their efficiency in [%].

Fig. 3. System boundaries of the LCA study.

Collected data refers to the main materials used in the production of

Table 1
these elements.
Input materials for manufacturing of the solar module containing 10 dye-
sensitized solar cells.
Collating the LCIA on the basis of production data that refer to each
Input materials Amount Unit Comments of the materials used in construction, rather than on the basis of pro­
FTO TEC7 glass 20 piece 2.5 × 2.5 cm ducing specific elements
TiO2 paste 10 g 10% waste
Dye 0.004 g N719/juice/pomace/leaf
• Inventory data of the production stage of the TiO2 paste and N719
extract
EL-HSE high stability 0.01 mL dye were taken from secondary sources - scientific publications
electrolyte (Parisi et al., 2014) and additional documentation received from the
Platinum paste 0.001 g 10% waste authors. These data included the consumption of raw materials, en­
Ethanol 150 mL 140 mL waste
ergy, and waste and were collected for the separate synthesis steps of
Distilled water 1500 mL 1500 mL waste
N719 dye.
• Inventory data for the production of natural dyes were collected
During the use stage, no additional material or energy streams were based on laboratory tests carried out at the Institute of Quality Sci­
identified, and trouble-free operation of the system throughout the cell’s ence of the Poznan University of Economics & Business in 2019. As
lifetime was assumed. The balance of system (BOS) components were part of the data inventory, the process of freeze-drying the natural
not considered in the LCA analysis. Transport and installation of PV raw materials and dye preparation was included each time. For this
systems were also excluded from the LCA study. Due to the lack of access purpose, data on the consumption of lyophilisate, electricity, auxil­
to data related to the recovery and recycling of the analyzed products, iary materials, and waste were collected. Because chokeberry
the end-of-life of DSSCs was also not included in the LCA. Taking into pomace and leaves are waste from the food industry, the modeling
account the above-mentioned assumptions, it should be stated that the process for dye preparation included the bio-waste management
presented analysis shows an assessment of environmental impact in process.
cradle-to-gate scope. • Inventory data of module manufacturing were collected based on
direct measurements made at the Department of Engineering Mate­
rials and Biomaterials of Silesian University of Technology (Poland)
2.2. Inventory analysis
in 2019. The collected data relate to the consumption of cell com­
ponents, electricity, auxiliary materials, and waste. In the case of
The general input materials used to manufacture the solar module
ethanol waste, a distillation and recovery of 70% were assumed,
containing 10 dye-sensitized solar cells are presented in Table 1. Next,
while energy consumption was not included. Due to the unprofit­
the data sources are described.
ability of recovering other waste, incineration was used as the final
The inventory data for the LCA study was collected from both pri­
form of management.
mary and secondary sources:

In the LCA study, the ecoinvent database v.3.5 was used, and allo­
• Inventory data for platinum paste, EL-HSE high-stability electrolyte,
cation at the point of substitution (APOS) was applied. Data from the
and FTO TEC7 glass were taken from ecoinvent database v.3.5.

348
A. Błaszczyk et al.
secondary data set represented Polish or European technological
conditions.
The quality of the data was evaluated using a semi-quantitative
Pedigree Matrix approach proposed by Weidema and Wesnaes (1996),
where data quality indicators (DQI) were calculated for each inventory
element by taking into account several criteria: reliability, complete­
ness, temporal differences, geographical differences, and technological
differences.
The cumulative data quality collected for the LCA study are pre­
sented in Table 2. The presented indicator is an average sum of the DQIs
calculated for all inventory elements, where 1 means the lowest data
quality and 5 the highest. The cumulative quality of inventory data
collected for the module containing cells with natural dyes was deter­
mined to be 4.44. For the modules containing cells with N719 dye, the
cumulative data quality was 4.38.
2.3. 1. Reagents and equipment
Chokeberry pomace was freeze-dried using a TG15 lyophilizer
(Naturim, Wloclawek, Poland). Chokeberry leaves were freeze-dried
using an Alpha 1-2 LDplus lyophilizer (Martin Christ, Germany).
Lyophilized materials were milled with a KN 295 Knifetec mill.
Extraction was carried out using a Vibra-Cell ultrasonic processor
(130 W, 20 kHz).
An MS300FRO printing machine was used for printing TiO2 particles
and platinium layer. The prepared semiconducting layers were annealed
at 500 ◦ C for 30 min to remove the organic components of the paste in a
200 Miditherm MP furnace (Bego Company).
The current-voltage characteristics of DSSCs were measured using a
PV Test Solutions Tadeusz Żdanowicz Solar Cell I-V Tracer System with a
solar simulator and a Keithley 2400 source meter.
Methanol and ethanol were purchased from Avantor Performance
Materials (Gliwice, Poland). All chemicals and reagents were of
analytical grade.
The materials used to manufacture solar cells (FTO TEC7 glass, Pt
paste, EL-HSE high-stability electrolyte, and 18 NR-T titania paste) were
purchased from Sigma Aldrich. EL-HSE is redox couple I3‾/I‾ in 3-
methoxypropionitrile with additives such as: inorganic iodide salt,
organic iodide salt, imidazole compound.
2.3.1. Experimental section
2.3.1.1. Preparation of chokeberry samples
2.3.1.1.1. Preparation of chokeberry juice. Chokeberries (Aronia
melanocarpa), cultivar Nero were harvested in 2017 in Marwice, Poland.
The washed fruits were then pressed using a Sana Juicer EUJ-707R
(Omega, Poland) to obtain the chokeberry juice and pomace which
were then frozen. The prepared juice was stored at − 20 ◦ C until analysis.
The pomace was subjected to a freeze-drying process that consisted of
two stages: freezing at − 45 ◦ C and drying from 12 ◦ C to 48 ◦ C. The entire
drying process was carried out for 16 h and 15 min. The freeze-dried
chokeberry pomace was ground into a powder in a KN 295 Knifetec™
grinder.
2.3.1.1.2. Preparation of chokeberry pomace extract. 25 g of freeze-
dried chokeberry pomace was weighed and subjected to cold extrac­
tion three times (20 min each time). A fresh portion of 250 mL of 60%
ethanol solution was added each time. The constant parameters of the
extraction process were: temperature (25 ± 1 ◦ C), amplitude (50%), and
Table 2
Data quality assessment of analyzed DSSCs – expresses as Data Quality Rating.
DQR Module Module with Module with dyes Module with dyes
with N719 dyes from from chokeberry from chokeberry
dye chokeberry juice pomace extract leaf extract
4.38 4.44 4.44 4.44
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Solar Energy 215 (2021) 346–355
the ratio of the raw material mass to the amount of solvent (1:10) The
extraction process was carried out using a Vibra-Cell ultrasonic pro­
cessor (130 W, 20 kHz). The obtained extracts were filtered using a
sintered glass filtration set and then combined and concentrated using a
rotary evaporator at 30 ± 1 ◦ C while protecting the sample from light.
The concentrated extracts were transferred to 50 mL volumetric flasks,
which were filled with ethanol. The prepared extracts were stored at
− 20 ◦ C until analysis.
2.3.1.1.3. Preparation of chokeberry leaf extract. To 5.01 g of
lyophilized chokeberry leaves, 100 mL of methanol was added, and the
mixture was sonicated for 20 min at room temperature with a 50%
amplitude. During the second and third extraction stages, fresh solvent
was poured into the samples. After each step, the extracts were filtered
through a sintered glass filtration set. The obtained filtrates were com­
bined, and methanol was removed with a rotary evaporator (40 ± 1 ◦ C)
while protecting the sample from light. After drying under vacuum,
0.7315 g of a dark green solid was obtained.
2.3.1.2. Fabrication and characterization of DSSCs. The working and
counter electrode were obtained by screen printing TiO2 and
commercially-available platinum paste. Finally, the nanostructured
photoanodes were immersed in an anhydrous ethanol solution con­
taining 0.5 mM of dyes at room temperature without access to light.
Once removed, the electrode was washed with ethanol to remove excess
dye and allowed to dry. A sandwich-type solar cell was assembled by
placing a platinum-coated counter electrode on the working electrode
and then clipping them together. A few drops of EL-HSE high-stability
electrolyte were placed between the working and counter electrode. The
current–voltage characteristics of the dye-sensitized solar cells were
performed at standard test conditions (1000 W/m2 irradiance intensity,
25 ◦ C, AM1.5 spectrum) using a PV Test Solutions Tadeusz Żdanowicz
Solar Cell I-V Tracer System with a solar simulator and a Keithley 2400
source meter (Table 3). The intensity of the incident light was calibrated
by a National Renewable Energy Laboratory-certified silicon reference
cell equipped with a KG5 filter.
2.4. Environmental impact assessment – general information
The LCA study was conducted using the Impact 2002+ method
(Jolliet et al., 2003). This method combines midpoint and endpoint
approaches and enables to present the environmental impact, as cu­
mulative eco-indicators (normalized and weighted results), as well as
characterised impact category indicators (characterized results). The
LCA study conducted here analyzed 15 impact categories representing
specific environmental burdens. Environmental indicators with positive
values indicate a negative impact on environment, while a negative
value indicates an environmental benefit.
3. Results and discussion
Taking into account the total environmental impact expressed as
cumulative eco-indicator, a solar module made with N719 dye had the
highest environmental performance (Table 4). For the defined func­
tional unit, the total cumulative environmental impact of the module
with N719 dye was 15.44 mPt, and the cumulative eco-indicators ob­
tained for the modules with natural dyes were significantly higher.
Among the natural dyes, the module containing cells with dyes from
chokeberry juice displayed the highest environmental performance. The
worst was the module containing cells with dyes from chokeberry
pomace extract.
Table 5 presents weighted impact category indicators for analyzed
DSSCs for the defined functional unit. Based on obtained results, the
most relevant impact categories were identified. The most relevant
impact categories are described as the impact categories that cumula­
tively contributed to at least 80% of to the total environmental impact
A. Błaszczyk et al. Solar Energy 215 (2021) 346–355

Table 3
Photovoltaic parameters of fabricated DSSCs.
Dye Voc [V] Isc [mA] Jsc [mA/cm2] Vm [V] Im [mA] Pmax [W] FF [%] η [%]
Chokeberry juice 5.31 2.24 5.32 4.09 1.48 0.61 51.5 0.145
Chokeberry pomace extract 4.96 1.98 4.71 3.56 1.23 0.45 46.0 0.105
Chokeberry leaf extract 5.29 2.04 4.85 4.13 1.29 0.54 50.0 0.125
N719 6.99 4.82 11.47 4.86 4.31 2.09 62.5 5.060

the characterized results.

Table 4
The module with N719 dye generated 0.052 kg PM2.5 eq. per
Environmental impact assessment of analyzed DSSCs expressed as cumulative
defined functional unit. In the case of the module containing natural
eco-indicators (Single Scores).
dyes, the indicator values for Respiratory inorganics were much higher
Single Module Module with Module with Module with
(Fig. 4). Large differences in indicator values were observed also for the
Score with dyes from dyes from dyes from
[mPt] N719 dye chokeberry chokeberry chokeberry leaf other relevant impact categories.
juice pomace extract extract Greenhouse gas emissions during the life cycle of the module with
15.44 485.17 670.47 568.26
N719 amounted to 47.21 kg CO2 eq. (Fig. 5). For the module with nat­
ural dyes from chokeberry juice, greenhouse gas emissions in the life
cycle were 1521.42 kg CO2 eq. In the case of the module containing cells
based on the normalized and weighted results. For each of the analyzed with dyes from chokeberry leaf extract, the indicator value for Global
DSSCs modules, three identical relevant impact categories were identi­ warming was 20% higher. An even greater increase in the indicator value
fied: Respiratory inorganics, Global warming, and Non-renewable energy for this impact category was observed in the module containing cells
(Table 5). with dyes from chokeberry pomace extract.
Figs. 4–6 present the environmental impact of the analyzed DSSC The total primary energy for the module with N719 dye was 632.61
modules obtained for the most relevant impact categories expressed as MJ (Fig. 6). The indicator value for Non-renewable energy was almost

Table 5
Identification of the most relevant impact categories – based on normalized and weighted results of impact category indicators.
Impact Category Module with N719 Module with dyes from chokeberry Module with dyes from chokeberry pomace Module with dyes from chokeberry leaf
dye juice extract extract

mPt [%] mPt [%] mPt [%] mPt [%]

Carcinogens 0.13 0.83 4.15 0.86 5.74 0.86 4.86 0.85

Non-carcinogens 0.44 2.83 12.51 2.58 17.29 2.58 14.66 2.58
Respiratory inorganics 5.15 33.33 155.81 32.11 215.28 32.11 182.36 32.09
Ionizing radiation 0.00 0.03 0.15 0.03 0.21 0.03 0.17 0.03
Ozone layer depletion 0.00 0.00 0.00 0.00 0.01 0.00 0.01 0.00
Respiratory organics 0.00 0.01 0.07 0.01 0.09 0.01 0.08 0.01
Aquatic ecotoxicity 0.03 0.16 0.62 0.13 0.86 0.13 0.73 0.13
Terrestrial ecotoxicity 0.55 3.57 17.77 3.66 24.56 3.66 20.83 3.67
Terrestrial acid/nutrii 0.07 0.46 2.21 0.45 3.05 0.45 2.58 0.45
Land occupation 0.07 0.47 2.33 0.48 3.22 0.48 2.73 0.48
Global warming 4.77 30.88 153.66 31.67 212.38 31.67 180.17 31.71
Non-renewable energy 4.16 26.96 134.58 27.74 185.98 27.74 157.57 27.73
Mineral extraction 0.07 0.46 1.30 0.27 1.80 0.27 1.51 0.27

Module with N719 dye 0.05

Module with dyes from chokeberry juice 1.58

Module dyes from chokeberry pomace

2.18
extract

Module with dyes from chokeberry leaf

1.85
extract

0.00 0.50 1.00 1.50 2.00 2.50

Fig. 4. Environmental impact assessment of analyzed DSSCs – Respiratory inorganics. Results expressed as characterized impact category indicator [kg PM2.5 eq.].

350
A. Błaszczyk et al.
Module with N719 dye
Module with dyes from chokeberry juice
Module with dyes from chokeberry pomace
extract
Module with dyes from chokeberry leaf
extract
0 500
Fig. 5. Environmental impact assessment of analyzed DSSCs – Global warming. Results expressed as characterized impact category indicator [kg CO2 eq.].
Module with N719 dye
Module with dyes from chokeberry juice
Module with dyes from chokeberry pomace
extract
Module with dyes from chokeberry leaf
extract
0 5000 10000 15000 20000 25000 30000
Fig. 6. Environmental impact assessment of analyzed DSSCs – Non-renewable energy. Results expressed as characterized impact category indicator [MJ primary].
thirty times higher in the case of the module containing cells with dyes
from chokeberry juice. The total primary energy for the module with
chokeberry leaf extract was 17% higher than the module containing the
dye from the juice. Similar to the other two impact categories, the
highest impact for Non-renewable energy was observed for the module
containing cells with dyes from chokeberry pomace extract.
Analyzing two stages of the life cycle of compared DSSCs, it should
be noted that regardless of the dye type, the manufacturing of DSSCs was
definitely the main source of environmental burdens (Fig. 7). This stage
accounted for about 90% of the total environmental impact generated
by the module with natural dyes. The distribution of environmental
loads was different in the module with synthetic N719 dye. About 79%
of the environmental impact was assigned to the module manufacturing
stage, and about 21% to the component production stage.
Tables 6–8 present the characterized impact category indicators
obtained for the most relevant impact categories, with a breakdown into
two life cycle stages of the analyzed DSSCs.
The most important inventory element of the analyzed DSSCs was
the electricity consumed during module manufacturing (Fig. 8). For the
module with natural dyes, electricity was responsible for almost 85% of
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Solar Energy 215 (2021) 346–355
47.21
1521.42
2102.73
1783.87
1000 1500 2000 2500
632.61
20452.38
28264.82
23947.16
the total environmental impact per defined functional unit. Considering
the environmental loads of the module with N719 dye, electricity was
also a key element (about 75% of the total environmental impact). The
second critical point of this product was synthetic N719 dye, which
accounted for almost 12% of the total environmental impact per defined
functional unit. The eco-indicator assigned to the production of syn­
thetic dye amounted to 1.79 mPt per functional unit (Table 9). In the
case of chokeberry juice and chokeberry pomace extract, the environ­
mental impact of production was several times lower. For example, the
eco-indicator value for the production of dyes from chokeberry juice was
0.000493 mPt per functional unit. The large environmental impacts of
the chokeberry leaf dyes arose due to the comparatively high electricity
consumption during lyophilization.
Tables 10–12 present environmental impact of four dyes, that are
elements of the analyzed DSSCs, expressed as characterized results ob­
tained for the most relevant impact categories. In each of the three
relevant impact categories, the synthetic N719 dye performed worse
than the chokeberry juice and chokeberry pomace extract. The best re­
sults were obtained for the dyes from chokeberry juice. The indicator
value for Respiratory inorganics was 1.74E-06 kg PM2.5 eq. Greenhouse
A. Błaszczyk et al. Solar Energy 215 (2021) 346–355

Module with N719 dye 20.87 79.13

Module with dyes from chokeberry juice 10.49 89.51

Module with dyes from chokeberry

10.56 89.44
pomace extract

Module with dyes from chokeberry leaf

11.34 88.66
extract

0.00 20.00 40.00 60.00 80.00 100.00

Production of components DSSCs Manufacturing

Fig. 7. Environmental impact assessment of analyzed DSSCs – division into stages in the life cycle [%].

Table 6 Table 8
Environmental impact assessent of analyzed DSSCs – Respiratory inorganics. Environmental impact assessment of analyzed DSSCs – Non-renewable energy.
Results expressed as characterized impact category indicators [kg PM2.5 eq.]. Results expressed as characterized impact category indicators [MJ primary].
Stage in LC Module Module with Module with Module with Stage in LC Module Module with Module with Module with
with dyes from dyes from dyes from with dyes from dyes from dyes from
N719 chokeberry chokeberry chokeberry N719 chokeberry chokeberry chokeberry
dye juice pomace leaf extract dye juice pomace leaf extract
extract extract

Production of 0.01 0.26 0.35 0.31 Production of 94.41 1325.53 1851.55 1756.70
components components
[kg PM2.5 eq] [MJ primary]
DSSCs 0.04 1.32 1.83 1.54 DSSCSs 538.20 19126.85 26413.27 22190.46
Manufacturing Manufacturing
[kg PM2.5 eq] [MJ primary]

have higher environmental loads.

Table 7 As the energy efficiency of the analyzed modules is a key factor of the
Environmental impact assessment of analyzed DSSCs – Global warming. Results
environmental impact, the sensitivity analysis was conducted. Three
expressed as characterized impact category indicators [kg CO2 eq.].
different levels of efficiency were considered: ƞ = 1%, ƞ = 2%, ƞ = 5%.
Stage in LC Module Module with Module with Module with The results are presented as cumulative eco-indicators obtained for the
with dyes from dyes from dyes from
N719 chokeberry chokeberry chokeberry
previously defined functional unit (Fig. 9). Increasing the energy effi­
dye juice pomace leaf extract ciency of the modules based on natural dyes reduces the environmental
extract impact. When the value of energy efficiency of the modules based on
Production of 7.25 101.36 141.69 136.35 natural dyes will achieve 5%, their environmental performance will
components exceed the environmental performance of the module with N719
[kg CO2 eq] sensitizer. In this case, the total cumulative environmental impact of the
DSSCs 39.96 1420.06 1961.04 1647.52 best module based on natural sensitizer (from chokeberry juice) will be
Manufacturing
[kg CO2 eq]
14.07 mPt for the defined functional unit.

gas emissions were 0.001 kg CO2 eq., and the total primary energy was
0.015 MJ. In all of the analyzed impact categories, the dyes from the
chokeberry leaf extract performed the worst.
The key element in LCA studies is defining the functional unit, which
allows various product systems with similar functions to be compared.
In our LCA study, the DSSCs differed in the dye used, which directly
influenced the efficiency of the solar devices. The production of natural
dyes is much less environmentally damaging than synthetic dyes.
Nevertheless, the energy efficiency of the modules based on natural dyes
was so low, that for the implementation of the assumed functional unit
(generation of 1 kWh of electricity), a much larger surface of the module
was required compared with the module containing the synthetic dye.
For this reason DSSCs based on natural dyes from chokeberry extracts
4. Conclusions
In the literature, there is a belief that DSSCs based on natural dyes are
more environmentally friendly than those based on synthetic dyes
(Kumara et al., 2017). Therefore, the environmental performance of
different laboratory-produced dye-sensitized solar cells was assessed
“from cradle to gate” using a life cycle assessment. This study compared
the environmental impacts of DSSCs based on natural dyes from black
chokeberry with those of synthetic N719 dye. The analysis showed that
taking into account cradle-to-gate perspective the photovoltaic module
containing synthetic N719 dye had the highest environmental perfor­
mance, which was observed in all impact categories analyzed. Among
the modules containing natural dyes, the cells with chokeberry juice
dyes displayed the highest environmental performance. The lowest

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A. Błaszczyk et al. Solar Energy 215 (2021) 346–355

Module with N719 dye 11.59 75.03

Module with dyes from chokeberry juice 84.87

Module with dyes from chokeberry pomace extract 84.81

Module with dyes from chokeberry leaf extract 84.07

0 10 20 30 40 50 60 70 80 90 100

Dye TiO2 paste Platinum paste

Electrolyte FTO TEC7 glass Energy_Manufacturing
Water_Manufacturing Ethanol_Manufacturing Waste_Manufacturing
Wastwater_Manufacturing

Fig. 8. Environmental impact assessment of analyzed DSSCs – division into inventory elements [%].

Table 9
Environmental impact assessment of analyzed DSSCs – division into inventory elements. Results expressed as normalized and weighted indicators.
Inventory element Module with N719 Module with dyes from chokeberry Module with dyes from chokeberry pomace Module with dyes from chokeberry leaf
dye juice extract extract

Single Score [mPt]

Dye 1.79E+00 4.93E− 04 4.74E− 01 5.38E+00

TiO2 paste 3.11E− 05 1.10E− 03 1.52E− 03 1.28E− 03
Platinum paste 6.15E− 01 2.19E+01 3.02E+01 2.54E+01
Electrolyte 2.24E− 04 8.00E− 03 1.10E− 02 9.28E− 03
FTO TEC7 glass 8.17E− 01 2.90E+01 4.01E+01 3.37E+01
Energy_Manufacturing 1.16E+01 4.12E+02 5.69E+02 4.78E+02
Water_Manufacturing 1.11E− 02 3.95E− 01 5.45E− 01 4.58E− 01
Ethanol_Manufacturing 5.75E− 01 2.04E+01 2.82E+01 2.37E+01
Waste_Manufacturing 1.40E− 06 4.99E− 05 6.89E− 05 5.79E− 05
Wastwater_Manufacturing 4.69E− 02 1.67E+00 2.30E+00 1.93E+00

Table 10 Table 12
Environmental impact assessment of compared dyes – Respiratory inorganics. Environmental impact assessment of compared dyes – Non-renewable energy.
Results expressed as characterized impact category indicators [kg PM2.5 eq.]. Results expressed as characterized indicators of the impact category [MJ
Impact N719 dye Dyes from Dyes from Dyes from
primary].
Category chokeberry chokeberry chokeberry Impact N719 Dyes from Dyes from Dyes from
juice pomace leaf extract Category dye chokeberry chokeberry chokeberry leaf
extract juice pomace extract extract
Respiratory 7.72E− 03 1.74E− 06 1.19E− 03 1.62E− 02 Non-renewable 57.110 0.015 21.078 218.878
inorganics energy [MJ
[kg PM2.5 primary]
eq]

of natural dyes from black chokeberry.

Table 11
The most important factor influencing the environmental perfor­
Environmental impact assessment of compared dyes – Global Warming. Results mance of the compared products is their energy efficiency. The energy
expressed as characterized impact category indicators [kg CO2 eq.]. efficiency of the cells based on natural dyes was much lower than those
built with N719 dye. This means that analogous energy can be obtained
Impact N719 Dyes from Dyes from Dyes from
Category dye chokeberry chokeberry chokeberry leaf with a larger module area, which translates into material and energy
juice pomace extract extract consumption during manufacturing. The energy-consuming process
Global 4.399 0.001 1.723 18.761
during module production is so important during the life cycle of this
Warming product that it outweighs the environmental benefits of using natural
[kg CO2 sensitizers. Therefore, the production of natural dyes, despite being
eq] more environmentally effective, does not guarantee a greater environ­
mental efficiency of the overall module life cycle. Increasing the energy
efficiency of the modules based on natural dyes reduces certainly the
environmental performance was observed in the module with choke­
berry pomace dyes. The production of synthetic N719 dye as a single environmental impact. The sensitive analysis showed that when the
value of energy efficiency of the modules based on natural dyes will
inventory element has higher environmental impact than the production

353
A. Błaszczyk et al.
80
70.35 70.4 71.03
70
Environmental impact [pt]
60
50
40
30
20 15.44
10
0
ƞ - 1%
Module with N719 dye
Module with dyes from chokeberry pomace extract
Fig. 9. Environmental impact assessment of analyzed DSSCs expressed as cumulative eco-indicators (Single Scores) – sensitivity analysis.
achieve 5%, their environmental performance will exceed the environ­
mental performance of the module with N719 sensitizer.
Generally, the most important inventory element of the analyzed
DSSCs is the electricity consumed during the module production stage.
In laboratory conditions, it is difficult to reduce the energy consumption
during module manufacturing, so it cannot be ruled out that mass pro­
duction will enable the optimization of certain activities or an improved
energy balance.
DSSCs based on natural sensitizers are good candidates for sustain­
able solutions for future energy issues only when their efficiency is
improved. Further research should focus on improving the efficiency
and stability of DSSCs produced with natural dyes and identifying the
optimal DSSCs in terms of physicochemical parameters and a compar­
ative life cycle sustainability analysis. The optimization of the chemical
structures in the natural extracts by appriotiate isolation or modification
and the interfaces molecular engineering principles are possible strate­
gies to achieve these improvements.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
References
Ashok, A., Mathew, S., Shivaram, S., Shankarappa, S., Nair, S., Shanmugam, M., 2018.
Cost effective natural photo-sensitizer from upcycled jackfruit rags for dye sensitized
solar cells. J. Sci-Adv. Mater. Dev. 3, 213–220. https://doi.org/10.1016/j.
jsamd.2018.04.006.
Bignozzi, C.A., Argazzi, R., Boaretto, R., Busatto, E., Carli, S., Ronconi, F., Caramori, S.,
2013. The role of transition metal complexes in dye sensitized solar devices. Coord.
Chem. Rev. 257, 1472–1492. https://doi.org/10.1016/j.ccr.2012.09.008.
Błaszczyk, A., 2018. Strategies to improve the performance of metal-free dye-sensitized
solar cells. Dyes Pigm. 149, 707–718. https://doi.org/10.1016/j.
dyepig.2017.11.045.
Calogero, G., Yum, J.-H., Sinopoli, A., Di Marco, G., Grätzel, M., Nazeeruddin, M.K.,
2012. Anthocyanins and betalains as light-harvesting pigments for dye-sensitized
solar cells. Sol. Energy 86, 1563–1575. https://doi.org/10.1016/j.
solener.2012.02.018.
Calogero, G., Bartolotta, A., Di Marco, G., Di Carlo, A., Bonaccorso, F., 2015.
Vegetablebased dye-sensitized solar cells. Chem. Soc. Rev. 44 (10), 3244–3294.
https://doi.org/10.1039/C4CS00309H.
Calogero, G., Barichello, J., Citro, I., Mariani, P., Vesce, L., Bartolotta, A., Di Carlo, A., Di
Marco, G., 2018. Photoelectrochemical and spectrophotometric studies on dye-
sensitized solar cells (DSCs) and stable modules (DSCMs) based on natural
apocarotenoids pigments. Dyes Pigm. 155, 75–83. https://doi.org/10.1016/j.
dyepig.2018.03.021.
Solar Energy 215 (2021) 346–355
35.17 35.2 35.51
15.44 15.44
14.07 14.08 14.2
ƞ - 2% ƞ - 5%
Module with dyes from chokeberry juice
Module with dyes from chokeberry leaf extract
Chaurasia, S., Lin, J.T., 2016. Metal-free sensitizers for dye-sensitized solar cells. Chem.
Rec. 16, 1311–1336. https://doi.org/10.1002/tcr.201500288.
Erande, K.B., Hawaldar, P.Y., Suryawanshi, S.R., Babar, B.M., Mohite, A.A., Shelke, H.D.,
Nipane, S.V., Pawar, U.T., 2020. Extraction of natural dye (specifically anthocyanin)
from pomegranate fruit source and their subsequent use in DSSC. Materials Today:
Proceedings. https://doi.org/10.1016/j.matpr.2020.06.357.
Fakharuddin, A., Jose, R., Brown, T.M., Fabregat-Santiago, F., Bisquert, J., 2014.
A perspective on the production of dye-sensitized solar modules. Energy Environ.
Sci. 7, 3952–3981. https://doi.org/10.1039/C4EE01724B.
Fthenakis, V.M., Kim, H.C., 2011. Photovoltaics: life-cycle analyses. Sol. Energy 85,
1609–1628. https://doi.org/10.1016/j.solener.2009.10.002.
Greijer, H., Karlson, L., Lindquist, S.E., Hagfeldt, A., 2001. Environmental aspects of
electricity generation from a nanocrystaline dye sensitized solar cell system. Renew.
Energy 23, 27–39. https://doi.org/10.1016/S0960-1481(00)00111-7.
Iqbal, M., Ali, S., Khan, S., 2019. Progress in dye sensitized solar cell by incorporating
natural photosensitizers. Sol. Energy 181, 490–509. https://doi.org/10.1016/j.
solener.2019.02.023.
Jolliet, O., Margni, M., Charles, R., Humbert, S., Payet, J., Rebitzer, G., Rosenbaum, R.,
2003. IMPACT 2002+: a new life cycle impact assessment methodology. Int. J. Life
Cycle Assess. 8, 324–330.
Kakiage, K., Aoyama, Y., Yano, T., Oya, K., Fujisawa, J., Hanaya, M., 2015. Highly-
efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor
and carboxy-anchor dyes. Chem. Commun. 51, 15894–15897.
Kumara, N.T.R.N., Lim, A., Lim, C.M., Petra, M.I., Ekanayake, P., 2017. Recent progress
and utilization of natural pigments in dye sensitized solar cells: a review. Renew.
Sustain. Energy Rev. 78, 301–317. https://doi.org/10.1016/j.rser.2017.04.075.
Ludin, N.A., Mahmoud, A.-M.-A.-A., Mohamad, A.B., Kadhum, A.A.H., Sopian, K.,
Karim, N.S.A., 2014. Review on the development of natural dye photosensitizer for
dye-sensitized solar cells. Renew. Sustain. Energy Rev. 31, 386–396. https://doi.org/
10.1016/j.rser.2013.12.001.
Misra, A., Fischer, M.K.R., Bauerle, P., 2009. Metal-free organic dyes for dye-sensitized
solar cells: from structure: property relationships to design rules. Angew. Chem. Int.
Ed. 48, 2474–2499. https://doi.org/10.1002/anie.200804709.
Obi, K., Frolova, L., Fuierer, P., 2020. Preparation and performance of prickly pear
(Opuntia phaeacantha) and mulberry (Morus rubra) dye-sensitized solar cells. Sol.
Energy 208, 312–320. https://doi.org/10.1016/j.solener.2020.08.006.
Omar, A., Ali, M.S., Rahim, N.A., 2020. Electron transport properties analysis of titanium
dioxide dye-sensitized solar cells (TiO2-DSSCs) based natural dyes using
electrochemical impedance spectroscopy concept: a review. Sol. Energy 207,
1088–1121. https://doi.org/10.1016/j.solener.2020.07.028.
O’Regan, B., Grätzel, M., 1991. A low-cost, high-efficiency solar cell based on dye-
sensitized colloidal TiO2 films. Nature 353, 737–740. https://doi.org/10.1038/
353737a0.
Oszmiański, J., Wojdyło, A., 2005. Aronia melanocarpa phenolics and their antioxidant
activity. Eur. Food Res. Technol. 221, 809–813. https://doi.org/10.1007/s00217-
005-0002-5.
Parisi, M.L., Maranghi, S., Basosi, R., 2014. The evalution of the dye sensitized solar cells
from Grätzel prototype to up-scaled solar applications: a life cycle assessment
approach. Renew. Sustain. Energ. Rev. 39, 124–138. https://doi.org/10.1016/j.
rser.2014.07.079.
Parisi, M.L., Sinicropi, A., Basosi, R., 2011. Life cycle assessment of Gratzel-type cell
production for non conventional photovoltaics from novel organic dyes. Int. J. Heat
Technol. 29, 161–169.
Polo, A.S., Itokazu, M.K., Murakami Iha, N.Y., 2004. Metal complex sensitizers in dye-
sensitized solar cells. Coord. Chem. Rev. 248, 1343–1361. https://doi.org/10.1016/
j.ccr.2004.04.013.
354
A. Błaszczyk et al.
Prabavathy, N., Shalini, S., Balasundaraprabhu, R., Velauthapillai, D., Prasanna, S.,
Walke, P., Muthukumarasamy, N., 2017. Effect of solvents in the extraction and
stability of anthocyanin from the petals of Caesalpinia pulcherrima for natural dye
sensitized solar cell applications. J. Mater. Sci.: Mater. Electron. 9882–9892.
Ramamoorthy, R., Radha, N., Maheswari, G., Anandan, S., Manoharan, S., Williams, R.
V., 2016. Betalain and anthocyanin dye-sensitized solar cells. J. Appl. Electrochem.
46, 929–941.
Shalini, S., Balasundaraprabhu, R., Kumar, T.S., Prabavathy, N., Senthilarasu, S.,
Prasanna, S., 2016. Status and outlook of sensitizers/dyes used in dye sensitized
solar cells (DSSC): a review. Int. J. Energy Res. 40, 1303–1320. https://doi.org/
10.1002/er.3538.
Sharma, K., Sharma, V., Sharma, S.S., 2018. Dye-sensitized solar cells: fundamentals and
current status. Nanoscale Res. Lett. 13, 381. https://doi.org/10.1186/s11671-018-
2760-6.
Silva, C., Santos, A., Salazar, R., Lamilla, C., Pavez, B., Meza, P., Hunter, R.,
Barrientos, L., 2019. Evaluation of dye sensitized solar cells based on a pigment
obtained from Antarctic Streptomyces fildesensis. Sol. Energy 181, 379–385.
https://doi.org/10.1016/j.solener.2019.01.035.
Tabacchi, G., Fabbiani, M., Mino, L., Martra, G., Fois, E., 2019. The case of formic acid on
anatase TiO2(101): where is the acid proton? Angew. Chem. Int. Ed. 58,
12431–12434. https://doi.org/10.1002/anie.201906709.
Tian, Y., Liimatainen, J., Alanne, A.-L., Lindstedt, A., Liu, P., Sinkkonen, J., Kallio, H.,
Yang, B., 2017. Phenolic compounds extracted by acidic aqueous ethanol from
berries and leaves of different berry plants. Food Chem. 220, 266–281. https://doi.
org/10.1016/j.foodchem.2016.09.145.
355
Solar Energy 215 (2021) 346–355
Wang, X.-F., Matsuda, A., Koyama, Y., Nagae, H., Sasaki, S., Tamiaki, H., Wada, Y.,
2007a. Effects of plant carotenoid spacers on the performance of a dye-sensitized
solar cell using a chlorophyll derivative: enhancement of photocurrent determined
by one electron-oxidation potential of each carotenoid. Chem. Phys. Lett 423,
470–475. https://doi.org/10.1016/j.cplett.2006.04.008.
Wang, X.-F., Zhan, C.-H., Maoka, T., Wada, Y., Koyama, Y., 2007b. Fabrication of dye-
sensitized solar cells using chlorophylls c1 and c2 and their oxidized forms c1′ and
c2′ from Undaria pinnatifida (Wakame). Chem. Phys. Lett 447 (1–3), 79–85. https://
doi.org/10.1016/j.cplett.2007.08.097.
Wathon, M.H., Beaumont, N., Benohoud, M., Blackburn, R.S., Rayner, C.M., 2019.
Extraction of anthocyanins from Aronia melanocarpa skin waste as a sustainable
source of natural colorants. Color. Technol. 135, 5–16. https://doi.org/10.1111/
cote.12385.
Weidema, B.P., Wesnaes, M.S., 1996. Data quality management for life cycle inventories
— an example of using data quality indicators. J. Clean. Prod. 4, 167–174. https://
doi.org/10.1016/S0959-6526(96)00043-1.
Wu, X., Gu, L., Prior, R.L., McKay, S., 2004. Characterization of anthocyanins and
proanthocyanidins in some cultivars of ribes, aronia, and sambucus and their
antioxidant capacity. J. Agric. Food Chem. 52, 7846–7856. https://doi.org/
10.1021/jf0486850.
Yella, A., Mai, C.L., Zakeeruddin, S.M., Chang, S.N., Hsieh, C.H., Yeh, C.Y., Grätzel, M.,
2014. Molecular engineering of push-pull porphyrin dyes for highly efficient dye-
sensitized solar cells: the role of benzene spacers. Angew. Chem. Int. Ed. 53,
2973–2977. https://doi.org/10.1002/anie.201309343.
Zhang, L., Cole, J.M., 2015. Anchoring groups for dye-sensitized solar cells. ACS Appl.
Mater. Interfaces 7, 3427–3455. https://doi.org/10.1021/am507334m.